Halogenated acetal



Patented July 1, 1941 HALO GENATED ACETAL Joseph B. Dickey and James B.Normington, Rochester, N. Y., assignors to Eastman Kodak N. Y., acorporation of Company, Rochester New Jersey No Drawing. ApplicationJune 10, 1938, Serial No. 213,027

6 Claims.

This invention relates to halogenatedmixed acetals having groups ofunlike types on each branch of the acetal configuration.

Halogenated acetals have been employed as intermediates for thepreparation of useful com- Pounds such as acetals. However, previouslythe possibilities in the preparation of new and valuable compounds fromhalogenated acetals has been rather limited due to the similarity of thetype of the groups on each branch of the acetal fork of the compound. Noone has previously recognized that groups, different as to type andkind, could be present on the-two branches and that compounds of new andvaluable properties could be prepared therefrom.

One object of our invention is to provide halogenated acetals whichcontain groups unlike as to kind on the two branches of the acetal.Another object of our invention is to provide intermediates from whichmay be prepared new and useful compounds suitable for use as softeningagents or plasticizers, pharmaceuticals, dyes, lubricating agents, etc.

We have found that halogenated acetals may be prepared in which onebranch presents an alkyl group and the other branch presents aheterocyclic or alkoxyalkyl group, thus allowing much greater latitudein the preparation of useful chemical compounds than was previouslyconsidered possible. These halogenated acetals may be prepared bytreating e-p-dichloro or dibromo alkyl ether such as a-c-dichloroethylether with a hydroxy compound of tetrahydrofurfuryl or, of alkoxyalkyl in chemically equivalent amount either alone or preferably in thethe following formula:

presence of a suitable base only in sufficient amount to neutralize theH01 or I-IBr formed in the reaction.

Our halogenated acetals are represented by where R is a group, R is anaryl, heterocyclic or alkoxy alkyl group and X is a halogen atom. Thealkyl group may be methyl, ethyl, propyl, butyl or any other alkylespecially one selected from the lower members of the series.Tetrahydrofurfuryl is representative of the heterocyclic groups whichmay be present in the R position. The alkoxyalkyl may be methoxy ethyl,methoxy methyl, ethoxymethyl, ethoxy ethyl or in fact alkoxyalkyl groupsgenerally.

The following examples illustrate methods which may be employed toprepare our halogenated acetals:

Example I C2HaO This halogenated acetal a-methoxyethoxy fi bromoethylether boiled at 110115 C. at 12 'm'. in. pressure.

Example II 214 gms. of a-p-dichloroethyl ether was added dropwise to asolution of '34 gm. sodium dissolved in 230 gm. methoxy ethanol, keepingthe temperature at 10-15 C. The mixture was stirred at this temperaturefor 1 hour and then at room temperature for 2 hours. The saltwasfiltered out and the filtrate was distilled. A halogenated acetal,having the-following formula, was obtained in an yield:

OCHa

This compound u-methoxy ethoxy-p-chloroethyl ether boiled at -95 C. at12 m. m. pressure. u

Eazample III 66 gms. of potassium hydroxide was dissolved in 300 gms. oftetrahydrofurfuryl alcohol and this solution was added to 143 gms. ofa-fl-dichloroethyl ether at 10-l5 C. After filtration the filtrate wasdistilledto give the acetal which had the formula This halogenatedacetal a-tetrahydrofurfuryloxy-p-lchloroethyl ether, boiled at 118-119C. at 10 in. m. pressure.

tion or after it has proceeded, as this facilitates the recovery of thehalogenated acetal from the reaction mixture.

To avoid removal of the second halogen substituent of the dichloroethylether in the reaction, the amount of alcohol used should beapproximately chemically equivalent to the dihalogenated ether and theamount of base should be only enough to neutralize the H01 or HBr whichis formed in the reaction.

The halogenated acetals having unlike branches are valuable for thepreparation of commerically useful products. Yarn conditioning orsoftening agents may be prepared therefrom by reacting the halogenatedacetal with further alcohol and base or with an alkali metal alkoxideforming an acetal having the formula:

R being alkyl, R1 being alkyl, heterocyclic or substituted alkyl groupsand R2 being substituted alkyl, heterocyclic or aryl groups. Forexample, one mole of sodium is dissolved in two moles of .ethoxyethanoland this solution is treated while hot with one mole'of a methoxyethoxyp-chloroethyl ether. The mixture is stirred and refluxed for four hours.A product, having valuable yarn treating properties, is formed.

Another example of using one of these intermediates to prepare a yarntreating compound is as follows:

1 'mol of a-tetrahydrofurfuryloxy-c-chloroethyl ether is dissolved in 4mols of tetrahydrofurfuryl alcohol and heated on the steam bath. One molof solid potassium hydroxide is then added in small portions withshaking. Heating is continued for 5 hours to complete the reaction. Aproduct, having valuable yarn treating properties, is formed. 7

Our mixed halogenated acetals may be employed to form dye intermediates.For instance a-methoxyethoxy fl-chloroethyl ether is reacted withethylaniline in the presence of sodium carbonate in accordance with thefollowing equation:

N-QH2C OCgH4-OCH3 This dye intermediate, when reacted with diether.

Our mixed halogenated acetals are useful as intermediates for thepreparation of various compounds in which an acetal grouping, havingunlike branches, is desired. Due to the presence of the easilyreplaceable halogen, they may be readily reacted with compounds in whichlinkage takes place at this point, replacing the halogen and forming thehalogen acid or its salt as the by-product. 7

We claim:

1. A mixed halogenated acetal having the formula:

'mula:

R being an alkyl group and X being a member of the group consisting ofbromineand chlorine.

3. a-methoxy ethoxy -B-chloroethyl ether.

4. on tetrahydrofurfuryloxy p2 chloroethyl 5. A mixed halogenated acetalhaving the formula:

B being an alkyl group and B. being a member of the group consisting oftetrahydrofurfuryl and alkoxy alkyl groups. V I

JOSEPH B. DICKEYI f JAMES B. NORMINGTON,

CERTIFICATE OF CORRECTION. Patent No. 2,2Ln,l+s2,, July 1, 19m.

JOSEPH B. DICKEY, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,first colnmn, line 14.6, for the words "a group" read -a.n alkyl group";same line,

for "an aryl," read -.'a--; and that the said Letters Patent shouldberead with. this correction therein that the same mayoonform to therecord ofthe case in the Patent Office.

Signed and seeded this 21st day of October, A. D. 1914.1.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.

